Aviation fuel cold flow additives and compositions

ABSTRACT

Aviation fuel, such as jet fuel, blends and methods for improving cold flow properties of such fuels at extremely low temperatures are disclosed. Cold flow properties of, for example, JP-8+100 jet fuel, are improved by addition to the fuel of a polymer formed from polymerization of an α-olefin monomer or monomers. Demonstratable cold flow improvement of such fuels at temperatures of about −53° C. and lower is shown.

CROSS REFERENCE TO RELATED APPLICATION

This application is a continuation of U.S. patent application Ser. No. 10/459,841 filed Jun. 12, 2003 and claims the benefit of the filing date of the aforesaid application under 35 USC §120.

FIELD OF THE INVENTION

The invention pertains to jet fuel blends and methods in which a cold flow enhancement agent is added to the jet fuel to improve fuel flow rates and flow characteristics at low fuel temperatures.

BACKGROUND OF THE INVENTION

It is important that aviation fuel exhibits a freeze point that is sufficiently low to allow adequate fuel flow through fuel system lines and filters to the engine. It is known that fuel temperature decreases as flight time increases and that longer duration flights typically require lower freezing point fuels than do shorter duration flights.

Additionally, high altitude flights, such as those conducted under military operational conditions, also require lower freezing point fuels than do lower altitude conventional flights. Quite obviously then, there is a need to provide freeze point depressant/cold flow enhancement aids for aviation fuels, particularly for jet fuels, which will allow for sufficient fuel flow to desired combustion locations at the extremely low fuel temperatures encountered at high altitude and long duration flights. Publications WO 01/32811 A1 and WO 01/62874 A2 discuss details of aviation fuels and the need for lowered freeze point fuel blends.

One such means of enhancing the cold flow properties of wax containing hydrocarbon fluids is via chemical treatment. For example, use of poly-α-olefin to improve the cold flow properties of gas oil is taught by El-Gamal et al., J. of Polym. Sci., 61, pp. 1265-1272 (1966). The use of a low molecular weight highly branched polymers of normal α-olefin to improve the cold flow properties of residual fuel oil is taught in U.S. Pat. No. 4,022,590.

WO 01/62874 A2 teaches the use of various chemical additives to lower the freeze point of aviation fuels. It is further taught that certain classes of pour point additives known to those skilled in the art for treating middle distillates, such as heating oils and diesel fuels, are not necessarily effective in the treatment of aviation fuel and actually may be detrimental.

SUMMARY OF THE INVENTION

Methods for improving the cold flow rate of aviation fuels, and jet fuels in particular, are provided wherein the jet fuel is blended with a cold flow rate enhancement agent (CFREA). These are polymers of α-olefins. Any normal α-olefin having from about 6-22 C atoms may be employed in preparing the polymer of present invention. Exemplary α-olefin monomers include 1-decene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-octadecene, mixtures of any of the foregoing and the like. Preferably, the α-olefin monomer has 10 to 16 carbon atoms. Most preferred the α-olefin monomer is 1-dodecene.

The CFREAs of the invention may be used conjointly with an adjuvant treatment in the jet fuel. This adjuvant may comprise an oil-soluble, polar nitrogen-containing amine salt and/or amide.

DETAILED DESCRIPTION

In accordance with the invention, the CFREA comprises a polymer obtained by polymerization of an α-olefin. As stated above, the α-olefin preferably has about 10-16 carbon atoms.

The polymers of the present invention may be prepared via methods known to those skilled in the art, for example, see U.S. Pat. Nos. 2,937,129 and 3,149,178. These polymers can be linear polymers or highly branched polymers as taught in U.S. Pat. Nos. 4,022,590; 4,265,663; and 4,898,751. These patents are hereby incorporated herein by reference.

Preferred polymerized α-olefins are commercially available from Petrolite Corporation under the VYBAR® trade name. Particularly preferred as a cold flow additive for aviation fuel is VYBAR® 825. It is taught in U.S. Pat. No. 4,265,663 that VYBAR® 825 is prepared in accordance with the procedure of Example 3 of U.S. Pat. No. 2,937,129.

As would be understood by one skilled in the art in view of the present disclosure, it is intended that the aforementioned polymerization methods do not in any way limit the synthesis of the polymer of the present invention. Furthermore, it is to be understood that polymers comprising upward of 10 mole % of a branched olefin and/or isomerized olefin having from about 6 to 22 carbon atoms are also within the purview of the present invention.

The polymers of the present inventions should be added to an aviation fuel, for which improved cold flow performance is desired, in an amount effective for the purpose. In a preferred embodiment of the invention, the aviation fuel is selected from Jet Fuel A, Jet Fuel A-1, Jet Fuel B, JP-4, JP-8 and JP-8+100. Most preferably the jet fuel is a JP-8 based fuel such as neat JP-8 or the formulated JP-8+100.

Jet Fuel A and Jet Fuel A-1 are kerosene-type fuels with Jet Fuel B being a “wide cut” fuel. Jet A is used for many domestic commercial flights in the U.S. Most preferably, the CFREAs of the invention are used to increase the cold flow characteristics of military jet fuels such as JP-5, JPTS, JP-7, JP-8, and JP-8+100. JP-5 is currently used by the U.S. Navy with JP-8 and JP-8+100 used by the Air Force.

These fuel types are described in the following Table 1. TABLE 1 U.S. Military Jet Fuel Year Intro- Freeze Point Flash Fuel duced Type ° C. Max Point Comments JP-5 1952 Kerosene −46 60 JPTS 1956 Kerosene −53 43 High thermal stability JP-7 1960 Kerosene −43 60 Lower higher thermal stability JP-8 1979 Kerosene −47 38 U.S. Air Force JP-8 + 1998 Kerosene −47 38 U.S. Air Force 100 contains additives for improved thermal stability JP = jet propulsion Source: Chevron “Aviation Fuels” Technical Review.

The CFREA is preferably added to the jet fuel in an amount of about 1-7,500 mg/L of the jet fuel. More preferably, the CFREA is added in an amount of between about 200-5,000 mg/L, most preferably about 4,000 mg/L. The jet fuel/CFREA blend is capable of improving the cold flow rate of jet fuel, specifically, JP-8 based jet fuel, at fuel temperatures on the order of about −53° C. and below. Experimental results have indicated that the CFREAs when blended with JP-8 based jet fuel in accordance with the invention improve cold flow rates of the fuel so that they are, as measured in accordance with Table 2 and the test system described, on the order of about 0.50 (g/s) and greater at fuel temperatures of about −53° C. and lower.

The polymers of the invention can be employed in combination with conventional fuel additives such as dispersants, antioxidants, and metal deactivators. Such additives are known to those skilled in the art, for example, see U.S. Pat. Nos. 5,596,130 and 5,614,081.

The jet fuel cold flow enhancement agents are preferably used in combination with an adjuvant component comprising an oil-soluble polar nitrogen-containing compound. These are set forth in U.S. Pat. No. 4,211,534 (Feldman) incorporated by reference herein. Basically, as stated in the '534 specification, these compounds are oil-soluble amine salts and/or amides that are generally formed by reaction of at least one molar proportion of hydrocarbyl acid having 1-4 carboxyl groups or their anhydrides with a hydrocarbyl substituted primary, secondary, and/or tertiary amine.

In the case of polycarboxylic acids, or anhydrides, all of the acid groups may be converted to amine salts or amides, or part of the acid groups may be left unreacted.

The term “hydrocarbyl” as defined in U.S. Pat. No. 4,211,534 includes groups that may be branched or straight chain, saturated or unsaturated, aliphatic cycloaliphatic, aryl, alkaryl, substituted derivatives thereof and the like. Typically, these hydrocarbyl groups will consist of from about 4-24 carbon atoms, more preferably 10-20 carbon atoms. In general, the resultant compound should contain sufficient hydrocarbyl content so as to be soluble in the fuel matrix.

Exemplary hydrocarbyl substituted acids and anhydrides include, but are not limited to, hexanoic acid, lauric acid, palmitic acid, steric acid, behenic acid, benzoic acids, 1,2,4,5-benzenetetracarboxylic dianhydride, 1,2-cyclohexanedicarboxylic anhydride, ethylenediaminetetraacetic dianhydride, salicylic acid, succinic acid, succinic anhydride, alkenyl succinic anhydrides, polyisobutenyl succinic anhydrides (PIBSA), phthalic acids, phthalic anhydride, naphthenic acids, naphthenic anhydrides, and the like. Particularly preferred is phthalic anhydride.

The hydrocarbyl-substituted amines may be primary, secondary, or tertiary; preferably primary or secondary.

Exemplary hydrocarbyl substituted primary amines include, but are not limited to, coco amine, tallow amine, hydrogenated fatty primary amine, 2-ethylhexylamine, n-dodecyl amine, C₁₂₋₁₄ or C₁₆₋₂₂ tertiary alkyl primary amines from Rohm and Haas Company marketed under the trade name Primene®, mixtures thereof and the like. Particularly preferred is the C₁₆₋₂₂ tertiary alkyl primary amine marketed by Rohm and Haas Company under the trade name Primene® JM-T.

Exemplary hydrocarbyl substituted secondary amines include, but are not limited to, dicocoalkylamine, didecylamine, dioctadecylamine, ditallowamine, dihydrogenated tallowalkylamine, mixtures thereof and the like. Particularly preferred is dihydrogenated tallowalkylamine which is commercially available from Akzo Nobel Corporation under the trade name Armeen® 2HT.

As would be understood by one skilled in the art in view of the present disclosure, it is intended that the aforementioned examples do not in any way limit the description of the nitrogen-containing compounds. Furthermore, it is to be understood that ester analogs derived from a hydrocarbyl alcohol, and hydrocarbyl sulfo acid analogs such as those derived from o-sulphobenzoic acid or its anhydride, are also within the purview of the present invention.

An especially preferred group of polar nitrogen-containing compounds is the mixed amine salt/amides derived from reaction of hydrocarbyl acid (having two or more carboxyl groups) or its anhydrides as set forth above with a hydrocarbyl secondary amine. The resulting intermediate amide acid is then neutralized with a primary amine.

Generally, the preferred group of polar nitrogen-containing compounds can be represented by the formula

wherein Z is a divalent organic radical, R₁ and R₂ and R₃ are independently chosen from C₁₀-C₄₀ hydrocarbyl groups. The hydrocarbyl groups include straight or branched chain, saturated or unsaturated aliphatic, cyclonaliphatic, aryl or alkylaryl moieties. These hydrocarbyl groups may contain other groups or atoms such as hydroxy groups, carbonyl groups, ester groups, oxygen, sulfur, or chlorine groups. As stated above, the hydrocarbyl groups may be on the order of C₁₀-C₄₀ with the range of C₁₄-C₂₄ even more preferred. The R₁, R₂, and R₃ groupings can also represent mixtures of different hydrocarbyl groups. Preferably, R₃≠R₁ or R₂.

The resulting compound should contain sufficient hydrocarbon content to be oil-soluble.

The preferred oil-soluble, polar nitrogen-containing compound is prepared by initial reaction of a hydrocarbyl acid or its anhydride and a secondary amine, such as the Armeen® 2HT. Then, the resulting mixed amine salt/amide is neutralized with a primary amine such as the commercially available Primene® JM-T product. Approximately equimolar amounts of the reactants are used, resulting in a mixed substituted amide/amine salt.

The most preferred polar nitrogen-containing compound is an oil-soluble mixed amide/amine salt formed via reaction of equimolar amounts of phthalic anhydride with the secondary amine, Armeen® 2HT. The product of this reaction is then further reacted with an equimolar amount of the primary amine, Primene® JM-T to form benzoic acid, 2-[(bis(hydrogenated tallow alkyl)amino)carbonyl]-C₁₆-C₂₂ tert-alkyl amine salt having the structural formula:

wherein R₁ and R₂ are mixtures of C₁₆ and C₁₈ hydrocarbon from the commercially available tallowamine product, and R₃ is a mixture of C₁₈₋₂₂ hydrocarbons from the commercially available Primene® JM-T product.

The adjuvant nitrogen compounds can be used in amounts similar to those given above in conjunction with CFREA dosage.

The invention will be described further in conjunction with the following examples that are included for illustrative purposes only and should not be construed to limit the invention.

EXAMPLES

The poly[α-olefins] of the invention were dissolved in Aromatic 100 Solvent available from Exxon that is described as a light aromatic petroleum solvent comprising trimethylbenzene isomers, xylene isomers, n-propylbenzene and ethylbenzine. 25 wt % actives solutions were prepared. JP-8 jet fuel was then treated with a known amount of the additive solutions and subjected to cold flow testing. Tests were conducted using a Cold Additive Screening Test Apparatus (CAST) and a U-2 Wing Simulator Device.

In general, the CAST apparatus consists of two 500 ml flasks, one at atmospheric pressure and one sealed, connected via a ¼″ Teflon tube. A known amount of fuel is charged to the flask at atmospheric pressure and the apparatus is cooled to the desired test temperature in an environmental chamber. Once cooled to the desired temperature, vacuum (2″ Hg) is applied to the sealed flask. The effectiveness of an additive is determined by measuring the time it takes for the fuel to flow to the sealed flask, and the amount of fuel remaining in the atmospheric flask after the fuel flow ceases.

Screening results of the poly[α-olefins] of the present invention in the CAST apparatus are provided in Table 2 below. At approximately −53° C. the untreated fuel has solidified and exhibited 100% hold up and essentially no fuel flow. Additions of the additive of the present inventions to the fuel dramatically improved the cold flow properties at approximately −53° C. as evidenced by a substantial decrease in hold up and increase in fuel flow. It was further observed that substantial hold up was not observed until the fuel was cooled to approximately −55° C. TABLE 2 CAST Testing Results in JP-8 Fuel Conc. Fuel Hold Up Flow Rate Example CFREA mg/L* Temp ° C. % g/s Comparative None NA −53.5 100 NA 1 A 16,000 −53.5 5 0.91 2 ″ ″ −54.5 6 1.60 3 ″ ″ −55.1 18 1.22 4 ″ ″ −56.2 49 0.78 5 ″ ″ −57.2 65 0.53 6 ″ ″ −52.9 6 1.71 A = VYBAR ® 825 poly[α-olefin] *25 wt % actives solution

Description of the U-2 Wing Simulator Device is provided by Ervin, J. S. et al., “Investigation of the Use of JP-8+100 with Cold Flow Enhancer Additives as a Low-Cost Replacement for JPTS”, Energy & Fuels 13, 1246-1251 (1999). Screening results for the poly[α-olefins] of the present invention in the U-2 Wing Simulator Device is summarized in Table 3 below. At approximately −53° C. the untreated fuel exhibited significant hold up. Addition of the additive of the present invention to the fuel dramatically improved the cold flow properties at approximately −53° C. as evidenced by a substantial decrease in hold up. TABLE 3 U-2 Wing Simulator Testing Result in JP-8 Fuel Tank Initial Final Conc. Temp Weight Weight Hold up Example CFREA (mg/L)* (° C.) (lbs) (lbs) (%) Comparative None NA −49 196.5 192.0 2 Comparative None NA −52 198.0 107.2 46 7 A 16,000 −53 197.5 186.0 6 8 A 16,000 −55 197.7 152.5 23 9 A 16,000 −57 201.1 114.4 43 A = VYBAR ® 825 poly[α-olefin] *25 wt % actives solution

Additional tests were conducted on the CAST apparatus using the poly[α-olefin] by itself and in conjunction with an adjuvant treatment comprising the preferred oil-soluble, polar nitrogenous compound, as set forth above. Results are shown in Table 4 below. It was observed under certain conditions; e.g., Example 16, the performance of the blend exhibited better performance than the individual components on an equal dosage basis at comparable temperatures.

Additive B Preparation of Benzoic acid, 2-[(bis(hydrogenated tallow alkyl)amino)carbonyl]- C₁₆₋₂₂-tert-alkyl amine salt

To a four-necked reaction flask equipped with a mechanical overhead stirrer, thermocouple, reflux condenser, nitrogen sparge tube, addition port with septum and a heating mantle was added phthalic anhydride (99%, 5.0 g 0.03342 mole) and Armeen® 2HT (17.0 g, 0.03342 mole amine). The resulting wax mixture was then heated to 90° C. under nitrogen with mixing and held for four hours. Primene® JM-T (10.9 g, 0.03342 mole amine) was then added to the reactor at 90° C. over an eight-hour period, after which the batch was maintained at 90° C. for an additional four hours before cooling to room temperature to yield a wax like material. This wax was then diluted in Aromatic 100 to yield a 25 wt % solution of the nitrogen-containing compound.

Additive C Preparation of Benzoic acid, 2-[(bis(dodecyl)amino)carbonyl]- C₁₆₋₂₂-tert-alkyl amine salt

As in the preparation of Additive B except didocylamine was substituted for Armeen® 2HT on an equal molar basis. TABLE 4 CAST Studies in JP-8 Fuel Fuel Hold Flow Addi- Addi- Additive Conc. Temp up Rate Example tive 1 tive 2 Ratio (mg/L)* (° C.) (%) (g/s) Comparative None None — — −53.5 100 N/A 10 A — — 6,000 −52.9 6 1.71 11 A — — 16,000 −53.5 5 0.91 12 A — — 16,000 −55.1 18 1.22 13 A — — 16,000 −56.4 56 0.76 14 A — — 16,000 −57.2 65 0.53 — — B — 6,000 −53.0 10 0.68 — — B — 16,000 −53.3 9 0.93 15 A B 50/50 6,000 −53.3 36 1.09 — — C — 16,000 −54.5 70 0.26 16 A C 50/50 16,000 −55.1 9 1.00 A = VYBAR ®825 poly[α-olefin] B = Benzoic acid, 2-[(bis(hydrogenated tallow alkyl)amino)carbonyl]-C₁₆-C₂₂-tert-alkyl amine salt C = Benzoic acid, 2-[(bis(dodecyl)amino)carbonyl]-C₁₆-C₂₂-tert-alkyl amine salt *25 wt % actives solution

Low temperature viscosity studies of the treated fuel were carried out using a scanning Brookfield Viscometer in the temperature range of −5° C. to 60° C. as described by S. Zabarnich and M. Vangsness, Petroleum Chemistry Division Preprints 2002, 47(3), pp. 243-246 (2002). The results of this testing are given in Table 5. The knee temperature is defined as the temperature at which a rapid viscosity increase occurs due to crystal formation. It is desirable to have the “knee temperature” for a treated fuel to be shifted to a lower temperature relative to the neat fuel. It is also highly desirable to minimize the rate of viscosity increase as the fuel is cooled below the knee temperature. TABLE 5 Low Temperature Viscosity Results - Knee Temperature in JP-8 Fuel Additive Conc. Knee Example Additive 1 Additive 2 Ratio (mg/L)* Temp ° C. Comparative None None — — −52.0 A 6,000 −53.9 17 A — — 16,000 −55.7 — — B — 16,000 −54.0 18 A B 50/50 8,000 −55.3 19 A B 50/50 16,000 −56.5 A and B = same as in defined Table 4 *25 wt % actives solution

When the poly[α-olefin] CFREAs of the invention are conjointly used with an oil-soluble, polar nitrogenous adjuvant, both compounds can be provided in a convenient one drum approach, dissolved in a suitable organic solvent such as toluene, kerosene, HAN or the like. The polymeric CFREA is present in such compositions in a molar amount of about 0.01-100 moles CFREA to about 1 mole of the adjuvant. At present, it is preferred to use as the polymeric CFREA, VYBAR® 825, in conjunction with benzoic acid, 2-[(bis(hydrogenated tallow alkyl)amino)carbonyl]- C₁₆-C₂₂-tert-alkyl amine salt.

While the specification above has been drafted to include the best mode of practicing the invention as required by the patent statutes, the invention is not to be limited to that best mode or to other specific embodiments set forth in the specification. The breadth of the invention is to be measured only by the literal and equivalents constructions applied to the appended claims. 

1. Method of improving the cold flow rate of jet fuel comprising adding to said jet fuel an effective amount of the purpose of a cold flow rate enhancement agent (CFREA) comprising a polyolefin formed by polymerization of an α-olefin monomer having from about 6 to about 22 carbon atoms.
 2. Method as recited in claim 1 comprising adding from a 1-7,500 mg/L of said CFREA to said jet fuel, based upon 1 liter of said jet fuel.
 3. Method as recited in claim 1 wherein said jet fuel is JP-8 based jet fuel.
 4. Method as recited in claim 1 wherein said α-olefin is a member selected from the group consisting of 1-decene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-octadecene, and mixtures thereof.
 5. Method as recited in claim 4 wherein said α-olefin comprises 1-dodecene.
 6. Method as recited in claim 1 further comprising adding, as an adjuvant treatment to said jet fuel, about 1-7,500 mg/L of an oil-soluble, polar, nitrogen-containing compound to said jet fuel.
 7. Method as recited in claim 6 wherein said oil-soluble, polar, nitrogen-containing compound comprises an amine or amide.
 8. Method as recited in claim 7 wherein said oil-soluble polar nitrogen compound comprises a reaction product formed from reaction of a hydrocarbyl acid having two or more carboxyl groups and a hydrocarbyl secondary amine followed by neutralization of the resulting product with a hydrocarbyl primary amine.
 9. Method as recited in claim 6 wherein said oil-soluble, polar, nitrogen-containing compound is benzoic acid, 2-[(bis(hydrogenated tallow alkyl)amino)carbonyl]- C₁₆-C₂₂-tert-alkyl amine salt.
 10. Composition for improving the cold flow rate of jet fuel, said composition comprising, in an organic solvent medium, (1) a cold flow rate enhancement agent (CFREA) comprising a poly[olefin] formed by polymerization of an α-olefin monomer having from about 6 to about 22 carbon atoms and (2) an oil-soluble, polar, nitrogen-containing compound.
 11. Composition as recited in claim 10 wherein (1) is present in an amount of about 0.01-100 moles of (1) per 1 mole of (2).
 12. Composition as recited in claim 10 wherein said oil-soluble, polar nitrogen-containing compound is an amine salt and/or amide.
 13. Composition as recited in claim 12 wherein said oil-soluble, polar nitrogen-containing compound is a reaction product formed by reaction of a C₄-C₂₄ hydrocarbyl acid or anhydride thereof with a C₄-C₂₄ hydrocarbyl substituted primary, secondary and/or tertiary amine.
 14. Composition as recited in claim 14 wherein said oil-soluble, polar nitrogen-containing compound comprises a reaction product formed from reaction of a hydrocarbyl acid having two or more carboxyl groups or anhydride thereof and hydrocarbyl secondary amine followed by neutralization of the resulting product with a hydrocarbyl primary amine.
 15. Composition as recited in claim 10 wherein said oil-soluble, polar nitrogen compound is benzoic acid, 2-[(bis(hydrogenated tallow alkyl)amino)carbonyl]-C₁₆-C₂₂-tert-alkyl amine salt.
 16. Composition as recited in claim 15 wherein said α-olefin is a member selected from the group consisting of 1-decene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, and 1-octadecene and mixtures thereof.
 17. Composition as recited in claim 16 wherein said α-olefin comprises 1-dodecene.
 18. Method as recited in claim 3 wherein said JP-8 based jet fuel is subjected to temperatures of −53.0° C. and lower.
 19. Composition as recited in claim 10 wherein said composition comprises JP-8 jet fuel.
 20. Composition as recited in claim 19 wherein said composition is subjected to temperatures of −53.0° C. and lower. 